1) Balikesir University, Necatibey Education Faculty, Department of Chemistry, 10100 Balikesir; 2) TUBITAK, Marmara Research Center, MKTAE, PK.21, 41470 Gebze-Kocaeli; 3) Balikesir University, Science and Art Faculty, Department of Biology 10100 Balikesir; d) Istanbul University, Faculty of Pharmacy, 34452 Beyazit-Istanbul. Pablished in Khimiya Prirodnykh Soedinenii, No. 5, pp. 373-374, September-October, 2003. Original article submitted July 8, 2003.
0009-3130/03/3905-0453$25.00 ©
2003 Plenum Publishing Corporation 453
Chemistry of Natural Compounds, Vol. 39, No. 5, 2003
PHYTOCHEMICAL ANALYSIS OF SOME SIDERITIS SPECIES OF TURKEY
T. Kilic1, Ya. K. Yildiz1, A. C. Goren2, UDC 547.913
G. Tumen3, and G. Topcu1-4
Linearol, foliol, epicandicandiol, siderol and ent-7α,18-dihydroxy-15β,16β-epoxykaurane have been investigated for antibacterial activity test. Highest activity of epicandicandiol has been determined against E-coli.
Key words: Sideritis athoa, Sideritis trojana, Sideritis dichotoma, Sideritis Spilyea, Sideritis Argyrea, diterpenes, antibacterial activity.
Herbal parts of Sideritis athoa, Sideritis trojana, Sideritis dichotoma, Sideritis Spilyea, and Sideritis Argyrea which grow in the Balikesir region were investigated for their chemistry and biological activity. Dried aerial parts of the plants collected during flowering were successively extracted with hexane, acetone, and methanol. Diterpenes were isolated and characterized from the extracts using choromato-spectral techniques. As a result 41 diterpenoids were isoleted from the five Sideritis species studied, corresponding to 27 single structures belonging to kaurene (1–24), beyerene (25), pimarene (26), and labdane (27) skeletons including the following five new kaurene diterpenes: ent-3β,7α-dihydroxykaur-16-ene (4), ent-7α ,17,18-trihydroxykaur-9,(11)-en-12-one (Athonolone) (9) from Sideritis athoa, ent-7α-acetoxy-15β,16β-epoxykaurane (16), 2α-hydroxy-8(14),15-pimaradiene (26) from Sideritis trojana, and ent-6β,8α- dihydroxylabda-13(16),14-diene (27) from Sideritis Argyrea (Table 1). Furthermore, linearol (1), foliol (2), 7-epicandicandiol (6), siderol (10), and ent-7α ,18-dihydroxy-15β,16β-epoxykaurane (20) compounds were used for antibacterial activity test [1–19].
Linearol (1), foliol (2), 7-epicandicandiol (6), siderol (10), and ent-7a,18-dihydroxy-15β,16β-epoxykaurane (20) compounds were used for antibacterial activity test. First, as a qualitative criterion, inhibition zones were characterized by the disc diffusion method for diterpenic compounds, and for inhibition zones greater than 7 mm, “tube dilution tests” were performed quantitatively. Bacillus subtilis, Staphylococcus aureus, Staphylococcus epidermidis, Proteus mirabilis, Escherichia coli, Enterococcus faecalis, and candida albicans were investigated, and MIC (minimum inhibitory concentration) values were found (Table 2). As a result, the highest activity from 7-epicandicandiol was observed against E. coli. In addition, the same compound was active against S. aureus, P. aeruginosa, K. pneumoniae, and E. faecalis. Ent-7α,18-dihydroxy-15β,16β -epoxykaurane (20) was moderately active against B. subtilis.
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TABLE 1. Isolated Diterpenes
No. Isolated Compound S. athoa S. trojana S. dichotoma S. sipylea S. Argyrea
Kauren Diterpenes 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. Linearol Foliol Sidol Ent-3β,7α-dihydroxykaur-16-ene Ent-3α,18-dihydroxykaur-16-ene 7-Epicandicandiol 7-Epicandicandiol 18 monoacetate Ent-3β-hydroxykaur-16-ene
Ent-7α,17,18-trihydroxykaur-9,(11)-en-12-one (Athonolone) Siderol Sideridiol Candol B Isocandol B Candol A acetate Ent-7α-acetoxykaur-15-ene
Ent-7α-acetoxy-15β,16β-epoxykaurane Ent-7α-acetoxy-18-hydroxykaur-16-ene Ent-7β,15α,18-trihydroxykaur-16-ene Ent-7β-acetoxy-15α,18-trihydroxykaur-16-ene Ent-7α,18-dihydroxy-15β,16β-epoxykaurane Ent-7α-acetoxy-18-hydroxy-15β,16β-epoxykaurane Isolinearol Isosidol Epoxyisolinearol + + + + + + -+ + -+ -+ + -+ + + + -+ + -+ + + + -+ -+ -+ + -+ + + + + + -+ + -+ + + -+ -Beyerene Diterpene 25. Ent-7α,18-dihydroxybeyer-15-ene + - + - -Pimarane Diterpene 26. 2α-Hydroxy-8(14),15-pimaradiene - + - - -Labdane Diterpene 27. Ent-6β,8α,dihydroxylabda-13(16),14-diene - - - - +
455 TABLE 2. Antibacterial (MIC) Activity Test Results for Linearol (1), Foliol (2), Epicandicandiol (6),
Siderol (10), and Ent-7α,18-dihydroxy-15β,16β-epoxykaurane (20)*,**
1 10 6 20 2 B. subtilis ATCC 6633 S. aureus ATCC 6538 Ps. Aeruginosa ATCC 9027 P. mirabilis ATCC 14153 E. coli ATCC K. pneumoniae ATCC 4352 E. faecalis ATCC 29212 C. albicans ATCC 10231 > 625 > 625 > 625 > 625 > 600 > 300 > 300 > 300 > 300 > 300 > 625 > 625 > 625 > 625 ______
*Minumum inhibition concentrations for compounds have been given as a mg/mL.
**it is performed by prof. Dr. C. B. Johansson (Marmara University, Department of Microbiology).
EXPERIMENTAL
Plant Material: Sideritis athoa, Sideritis trojana, Sideritis dichotoma, Sideritis Spilyea, and Sideritis Argyrea were collected from the Kazdagi region in June 1995. The plants were identified by Prof. Dr. K. H. C. Baser (Eskisehir); a voucher specimen was deposited in the Herbarium of the Faculty of the Pharmacy, Anadolu University.
General: The spectra were recorded with the following instruments: IR: Perkin–Elmer 980 in CHCl3; NMR: Bruker AC-200 L, 200 MHz and 50.32 MHz for 1H and 13C-NMR, respectively, in CDCl3; HRMS: VG ZabSPEC (maximum mass resolution 10.000). For isolation and purification of the compounds TLC: Kieselgel 60F254 (E.Merc) precoated plates, CC: Silicagel 60 and Sephadex LH-20 (Fluka) were used.
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